S-(4-Chlorobenzyl)-N,N-Diethylthiolcarbamate

ABSTRACT

This invention relates to a novel compound of S-(4chlorobenzyl)-N,N-diethylthiocarbamate, which is useful as an active ingredient of herbicidal composition, a feed additive for growing chicken and a fungicide for sclerotium of Pellicularia Oryzae.

United States Patent 1191 Konnai et a1.

[ 1 Oct. 21, 1975 S-(4-CHLOROBENZYL)-N,N-DIETHYLTHI- OLCARBAMATE [75] Inventors: Makoto Konnai, Ogasa; Hiroshi Kamata; Masaru Kado, both of Shimizu, all of Japan [73] Assignee: Kumiai Chemical Industry Co., Ltd.,

Tokyo, Japan [22] Filed: Nov. 5, 1973 [21] Appl. No: 412,898

Related US. Application Data [63] Continuation-impart of Ser. No. 123,881, March 12, 1971, Pat. No. 3,846,115, which is a continuation of Ser. No. 19,546. March 19, 1970, Pat No. 3,582,314. which is a continuation of Ser. No. 651.148. July 5. 1967, abandoned.

[30] Foreign Application Priority Data Feb. 11), 1967 Japan v I 42-8153 Mar. 27. 1967 Japan 42-18774 52 us. C1 2 60/455 A {51] Int. Cl. C07C 155/02 [58] Field of Search 260/455 A Primary ExaminerLewis Gotts Assistant Examiner-D. R. Phillips Attorney, Agent, or FirmStevens, Davis, Miller & Mosher [57] ABSTRACT This invention relates to a novel compound of S-(4- chlorobenzyl)-N,N-diethylthiocarbamate, which is useful as an active ingredient of herbicidal composition, a feed additive for growing chicken and a fungicide for sclerotium of Pellicularia Oryzae.

1 Claim, 1 Drawing Figure US. Patent Oct. 21, 1975 f aououjujsuw S-(4-CHLOROBENZYL )-N,N-DIETHYLTHIOLCAR- BAMATE This application is a continuation-impart of the copending application Ser. No. 123,881, filed Mar. 12,

l971;now U.S. Pat. No. 3,846,115, which is a continu a'tion application of application Ser. No. 19,546, filed Mar. 19, 1970, now U.S. Pat. No. 3,582,314, which is a continuation application of application Ser. No. 651,148 filed July 5, 1967, now abandoned.

It is an object of the present invention to provide a novel compound of S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate.

The novel compound of S-(4-chlorobenzyl)-N,N- diethylthiolcarbamate has a boiling point of 128-136C/0.02 mmHg and a refractive-index of n 1.5632. An infrared spectrum of S-(4-chlorobenzyl)- N,N-diethylthiolcarbamateis shown in the drawings- (4-chl'orobenzyl)-N,N-diethylthio1carbamate h'as LDSO value of 1,300 mg/kg for rat and LDSO value of 2,400 mg/kg for mouse, which are of remarkably low toxicity.

The following example is a typical preparation of useful S-(4-chl0robenzyl) N,N-diethylthiolcarbamate.

EXAMPLE .1

A solution of 31 g (0.2 mol) of 4-chlorobenzylmercaptan in 100 ml of toluene was mixed with 70 g (about 0.2 mol) of 30% solution of phosgene in toluene. To the resulting mixture were added dropwise 24.2 g (0.2 mol) of dimethylaniline while stirring under cooling with ice maintaining the temperature below C.

After addition'of the said dimethylanilifie, the mixture was stirred for one hour while maintaining such a condition and was added dropwisewith 29.2 g (0.4 mol) of diethylamine at a temperature of lower than C. Furthermore, the resulting mixture was stirred at room temperature for 1 hour and then at about 60C for 3 hours to complete the reaction, and then the temperature was returned to room temperature. After the reaction, the formed dimethylaniline hydrochloride was removed by washing with water and organic layer,

Elemental Calculated Found analysis value value EXAMPLE 2 A mixture of 13.5 g(0.1 mol) of diethylcarbamoyl chloride, 15.9 g (0.1 mol) of p-chlorobenzylmercaptan, 150 ml of xylene and 0.1 ml of diethylaniline was heated at 100C for 5 hours with the vigorous stirring. After cooling, the xylene layer was washed with water.

The xylene was removed after drying over anhydrous sodium sulfate.

The resulting liquid was purified by vacuum distillation to obtain 24.3 g (yield: 94.5%) ofa transparent liquid having a boiling point of 129136C/0.01 mmHg and a refractive index of n 1.5634.

EXAMPLE 3 A 200 ml of four-necked flask was equipped with stirrer, condenser, thermometer and gas inlet tube. A mixture of 7.3 g (0.1 mol) of diethylamine and 4.0 g (0.1 mol) of sodium hydroxide in ml of water was charged into the flask, and then 6.6 g (0.1 mol) of carbonyl sulfide was introduced in the mixture at 05C over 4 hours under the vigorous stirring.

After the introduction of carbonyl sulfide, the reac tion mixture was stirred at O5C for 2 hours. The mixture was diluted with 50 ml of acetone, and 20.5 g (0.1 mol) of p-chlorobenzyl bromide was added into the reaction mixture at 5-10C.

After the addition ofp-chlorobenzyl bromide, the reaction mixture was stirred at 56 65C for 5 hours, and the acetone was removed. The residue was extracted with 200 m1 of benzene and washed with water. The benzene was removed after drying over anhydrous sodium sulfate. The resulting liquid was purified by vacuum distillation to. obtain 25.0 g (yield: 97.0%) of a transparent liquid having a boiling point of 128-l36C/0.02 mmHg and a refractive index of m S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate according to thepresent invention is useful as an active ingredient of herbicidal composition and a feed additive for growing chicken and a fungicide for sclerotium of Pellicularia Oryzae.

In order to show superior effect of S-(4- chlorobenzyl)-N,N-diethylthiolcarbamate over the known compounds, the following comparative tests were carried out. (Test 1) Growth promoting effect for growing chicken:

Table 1 Average weight and feed efficiency:

Avera e wei ht( Active Group ingredient lnitial After After Rate of in feed 4 8 weight Feed (ppm) weeks weeks gain efficiency 1 none 42 530 1.706 100.00 2.45 2 10 42 386 1,753 102.76 2.40 3 5O 42 588 1,790 104.92 2.34 4 42 591 1,835 107.56 2.33 5 200 42 593 1.860 2.29

The remarkable growth improving effect of S-(4- chlorobenzyl)-N,N-diethylthiolcarbamate was confirmed. No decrease of weight of chicken was found by feeding a large amount of S-(4-chlorobenzyl)-N,N-

diethylthiolcarbamate.

Table 2 Table 3 Continued Composition of basal feed:

Premix of Vitamin and Mineral in basal feed. Vitamin and Mineral in of e this Table are added in basal feed as premix Start Finish 5 (in l kg feed) -4 weeks 48 w ks Element Start Finish Yellow Corn 42.6 43.0 Cobalt (H. 5 mg Milo Meal 20.0 20.6 Soybean Meal 19.0 8.0 Zmc mg Rusan Meal 2.0 2.0 Fish Soluble 2.6 2.4 (Test 2) Fish Meal 6.0 9.5 Sesame Meal Tests of weed control activity and rice phytotoxicity: Salli lfcedc b 2 4 2 Test method: z Sandy soil (clay content: about 10%), loam (clay y s 0-5 0.5 content: about 30%), and clay loam (clay content:

Phmphme I5 about 70%) were fed in porcelain pots having a diameter of cm. respectively, and then each pot was 1040 flooded with water to a depth of 3 cm. Thereafter, l0

Premix contains mineral and vatamin are shown in Table 3.

Table 3 Premix of Vitamin and Mineral in basal feed. Vitamin and Mineral in this Table are added in basal feed as premix rice plants of Z-Ieaf stage (variety: KINMAZE) were planted in theeach pot, and 24 hours later 50 seeds of Barnyardgrass, Echinochloa vcrus-galli and Konagi, Monochoria vaginalis per pot were sowed thereon.

Threedays later, a test solution prepared by diluting a given amount of a 25% wettable power of active ingredient shown in the following Table 4 with 10 ml of (in I kg'feed) Element Sm" Finish water was uniformly dropped on the water surface in the pot..Twenty days after the treatment, the inhibition vitamin A 6,000 3.000 lU rate against Barnyardgrass and Konagi and phytotoxic- Vitamin D 1,200 600 IU dd I d t d Vitamin E 026 0 13 [U ity on pa y rice p ant were e ermine Vitamin B, i.0 0.5 mg The said 25% wettable powder was prepared as fol- Vitamin B2 6.0 3.0 mg Vitamin B, 2.0 i.0 mg lows Pantothenic Acid 9.0 mg Twenty five parts by weight of thiocarbamate, 10 Nico mic Aciii 14.0 7.0 mg parts by weight of white carbon, parts by weight of Choline Chloride 300.0 150.0 mg f Folic Acid 0}] 0.05 mg diatomaceous earth and 5 parts by weight 0 wetting Manganese 1200 g agent of a mixture of polyoxyethylenealkyl phenol ggg g'g 3g :5 35 ether, polyoxyethylenephenol ether and polyoxyethyl- Iodine 1.0 0.5 v mg ene carbonate were mixed and milled.

Table 4 I Sandy Soil Loam Clay Loam I Dosage f Inhibition Phytov Inhibition Phyto- Inhibition Phyto- Active Ingredient in Active rate toxicity rate toxocity rate toxicity Ingredient Barn- Paddy Barn- Paddy Barn- Paddy (g/IO a) yard- Konagi rice -yard- Konagi rice yard- Konagi rice grass plant grass plant grass plant Present Invention 0 2" II 400 s s 5 5 5 5 NCSCH,- z s I00 5 4 5 4 5 4 u.s. Pat. No. 2,992,091

S isoC;,I-I II 400 4 4 H 3.5 3.5 3 3.5

NCS-CH -QCI iso-C H, 2 2 1 2 I s 2 isoC H 400 4 4.5 4+ 3.5 3.5 3 3.5

Ncs-ci-i,- l isoC H I00 2 2 l 2 I 1.5

C iso-C;,H 1 400 4.5 4.5 H- 3.5 4 3 3.5

N S-CI-I -Cl isoC I-I 100 2 3 I 2 I I S is0C; H 400 4 4 3+ 3 3.5 2.5 3

N s ci-i is0C -,H 100 2 2 I v 2' 0 I s iSo CnH1 1]: cl 400 3.5 3 2.5 2 r 2 2 NCS- i-i Cl isi C H c 100 1.5 1 0 0 0 0 Table 4 Continued.

Sandy Soil Loam Clay Loam Dosage Inhibition Phyto- Inhibition Phyto- Inhibition Phyto- Activc Ingredient in Active rate toxicity rate toxocity rate toxicity Ingredient Bam- Paddy Barn- Paddy Barn- Paddy (g/lO a) yard- Konagi rice yard- Konagi rice yard- Konagi rice grass plant grass plant grass plant S CH II 400 4.5 4.5 4.5 4 4 4 NCS-CHFO CH I00 3 2.5 2 2 2 2 C,H if CI 400 3.5 2.5 3 2 1 3 2 NCS-CH1-Q 3 0 H, 100 1.5 I l o 1 0 O isn-QH, c 400 s 3 i 2.5 2.5 2 2 PNCS-CH 3 is0-C H I00 I l 0 0 0 0 Australian Patent 272,77l 0 Cl lhO-CaH-r II 400 s s 5 4.5 +4- 4.5 4.5 I -cs c lS0-C H c I00 3 5 3 3 3 2.5 2.5

iso-C If 400 5 4.5 -H-l- 4.5 4' -H- 4.5 4

NCS-CH; is0--C H Cl 100 3 2.5 2.5 2 2.5 2

O -i+- iso--C H-, H 400 5 4.5 5 4 4+ 4.5 3.5

NCS-C isoC,-,H 100 3 2 i 2 5 2 2 L5 c iso-QH, W 400 2.5 2.5 i 2.5 2 2 H -cs c|i.. isoC c I00 0 I 0 0 0 0 o iso-C;H 400 s 4.5 -H-+ 5 4.5 5 4 Ncs-c iso-C 100 4 4 2 1 3.5 2

. n-CJ-I if 400 5 4 -ll- 4 5 3.5 -H- 4.5 3.5

NCS-C n-C.H, I00 3 2 2 l 2 1 Blank sample 0 0 0 0 0 0 Untreated 0 0 0 0 0 O Note: In the above described preparation of the wettable powder, the active ingredient was removed. that is. this composition consisted of white Inhibition of germination of sclerotium of Pellicularia Fifty g sclerotium having diameter of 1.5-2.0 mm which was collected from a paddy field wherein Pellicularia Oryzae had been caused in the former year, were wrapped in a gauze and dipped in the following solution.

carbon, diatomaceous earth and wetting agent.

(Test 3) Phytotoxicity +-H- severe damage no damage The dipping time and the concentration of the ingredients are shown in Table 5. After dipping, the gauze wrapping sclerotium was washed with flowing water for 24 hours to remove the ingredient on the surface of sclerotium. The treated sclerotium were placed on 'a glass plate and put in a sealed vessel and were cultured at 27C for 72 hours under the saturated humidity, and then a rate of germination of the sclerotium was deter- Oryzae 55 mined. The results are shown in Table 5.

Table 5 Coneen- Dipping Rate of Ingredient tration time Germination p (hr) (7r) Present Invention is0-C,H j

N S-CH -GCI 10 24 so Isa-C ll, 

1. S-(4-CHLOROBENZYL)-N,N-DIETHYLTHIOLCARBAMATE. 